JPWO2019198705A1 - Antifouling paint composition - Google Patents

Abstract

Anti-fouling coating with high environmental safety, capable of exhibiting good anti-fouling performance even in the draft area where dissolution of the coating film continues for a long time even after exposure to sunlight for a long time and aquatic fouling organisms are likely to attach A composition for forming a film is provided. According to the present invention, there is provided an antifouling coating composition containing a copolymer A, a copolymer B, and an antifouling agent, wherein the copolymers A and B are each a single amount. It is obtained by copolymerizing a mixture of the body (a) and the polymerizable unsaturated monomer (b) other than the monomer (a), and the monomer (a) is represented by the general formula (1). Represented by the general formula (1): (wherein, R1 is hydrogen or a methyl group, R2, R3, and R4 are selected from a branched alkyl group having 3 to 8 carbon atoms and a phenyl group; Also, the copolymer A satisfies the following requirements (A1) to (A2), and the copolymer B satisfies the following requirements (B1) to (B2). Will be provided. (A1) The content of the monomer (a) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b). (A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b). . (B1) The content of the monomer (a) is 30 to 40 mass% with respect to the total mass of the monomer (a) and the monomer (b). (B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b). .

Description

The present invention relates to an antifouling coating composition.

  Aquatic fouling organisms such as barnacles, serpra, mussels, hemlock worms, ascidians, sea squirts, sea lions, slimes, etc., are used in underwater structures such as vessels (especially the bottom of the ship), fishing nets, fishing net accessories, and power plant water pipes. The adhesion causes problems such as impairing the functions of the ships and the like, and impairing the appearance.

  In order to prevent such problems, an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and the antifouling agent is gradually released from the antifouling coating film, so that the antifouling coating agent can be treated for a long period of time. A technique for exerting performance is known (Patent Document 1).

JP, 2000-17203, A

  However, even if the technique of Patent Document 1 is adopted, the coating film portion that is always submerged in seawater maintains long-term antifouling performance, but in the draft section that is the boundary between water and above water, dry and There is a problem that the antifouling property is not sufficiently exerted because it is repeatedly wet and is affected by various factors such as being easily affected by sunlight.

  The present invention has been made in view of such circumstances, good coating film dissolution is continued for a long period of time even after being exposed to sunlight for a long time, and is also good in a draft section where aquatic fouling organisms are likely to adhere. The present invention provides a composition for forming an antifouling coating film having high environmental safety and capable of exhibiting excellent antifouling performance.

According to the present invention, there is provided an antifouling coating composition containing a copolymer A, a copolymer B and an antifouling agent, wherein the copolymers A and B are each a monomer (a). And a mixture of a polymerizable unsaturated monomer (b) other than the monomer (a), and the monomer (a) is represented by the general formula (1):
General formula (1):

(In the formula, R ¹ is hydrogen or a methyl group, R ² , R ³ , and R ⁴ are selected from a branched alkyl group having 3 to 8 carbon atoms and a phenyl group, and may be the same or different.)
The copolymer A satisfies the following requirements (A1) to (A2),
The copolymer B provides an antifouling coating composition that satisfies the following requirements (B1) to (B2).
(A1) The content of the monomer (a) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).
(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b). .
(B1) The content of the monomer (a) is 30 to 40 mass% with respect to the total mass of the monomer (a) and the monomer (b).
(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b). .

  As a result of intensive studies by the present inventor, a copolymer A obtained by copolymerizing a mixture containing a silyl ester monomer and 2-methoxyethyl acrylate in specific amounts, a silyl ester monomer and methacryl When an antifouling coating film was formed using a composition containing the copolymer B obtained by copolymerizing a mixture containing 2-methoxyethyl acid in a specific amount, good antifouling performance is exhibited even in a draft section. The present invention has been completed and the present invention has been completed.

  Hereinafter, the present invention will be described in detail.

1. Antifouling Paint Composition The antifouling paint composition of the present invention contains a copolymer A, a copolymer B, and an antifouling agent.

1-1. Copolymers A and B
Each of the copolymers A and B is a (meth) acrylic acid triorganosilyl ester copolymer, and includes a monomer (a) and a polymerizable unsaturated monomer other than the monomer (a) ( It is obtained by copolymerizing the mixture of b). Therefore, the copolymers A and B contain the monomer units derived from the monomers (a) and (b), respectively. The compounds contained in the monomer (a) and the compounding ratio thereof may be the same or different between the copolymers A and B. The compounds contained in the monomer (b) may be the same or different in the copolymers A and B. When the compounds contained in the monomer (b) are the same in the copolymers A and B, the compounding ratios are different.

<Monomer (a)>
The monomer (a) is a (meth) acrylic acid triorganosilyl ester monomer and is represented by the general formula (1).

General formula (1):
(In the formula, R ¹ is hydrogen or a methyl group, R ² , R ³ , and R ⁴ are selected from a branched alkyl group having 3 to 8 carbon atoms and a phenyl group, and may be the same or different.)

  In the present invention, examples of the monomer (a) represented by the general formula (1) include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, and tris-methacrylic acid s-. Butylsilyl, triisoamylsilyl (meth) acrylate, tris (2-ethylhexyl) silyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropylisobutylsilyl (meth) acrylate, diisopropylisoamylsilyl (meth) acrylate , (Meth) acrylate diisopropyl (2-ethylhexyl) silyl, (meth) acrylate diisopropylphenylsilyl, (meth) acrylate diisopropylcyclohexylsilyl, (meth) acrylate t-butyldiisopropylsilyl, (meth) acrylate t- Butyldi Sobutylsilyl, t-butyldiisoamylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and the like are preferable, and triisopropylsilyl (meth) acrylate is particularly preferable, and triisopropyl methacrylate is particularly preferable. It's Cyril. These monomers are used alone or in combination of two or more.

<Monomer (b)>
The monomer (b) is a monomer copolymerizable with the monomer (a), and examples thereof include the following. Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 21-ethylhexyl (meth) acrylate, Phenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, (Meth) acrylic acid ester such as diethylaminoethyl (meth) acrylate Kind.
Zinc (meth) acrylate versatate, Magnesium (meth) acrylate versatate, Copper (meth) acrylate versatate, Zinc (meth) octylate acrylate, Magnesium octylate (meth) acrylate, Copper octylate (meth) acrylate, Lauric acid (Meth) such as zinc (meth) acrylate, magnesium (meth) acrylate laurate, copper (meth) acrylate laurate, zinc (meth) acrylate stearate, magnesium (meth) acrylate stearate, copper (meth) acrylate stearate Metal (meth) acrylates such as metal acrylate pendants, zinc (meth) acrylate, and copper (meth) acrylate.
Vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.
Aromatic compounds such as styrene, vinyltoluene and α-methylstyrene.
Dialkyl ester compounds of unsaturated dibasic acids such as dimethylmalate, dibutylmalate, and dimethylfumarate.

  The monomer (b) is used alone or in combination of two or more, and preferably (meth) acrylic acid esters.

<Requirements (A1) to (A2) and (B1) to (B2)>
In the present invention, it is essential that the copolymer A satisfies the requirements (A1) to (A2) and the copolymer B satisfies the requirements (B1) to (B2).

The content of the monomer (a) (A1) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).
The content of 2-methoxyethyl acrylate in the monomer (b) (A2) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b).
The content of the monomer (a) (B1) is 30 to 40 mass% with respect to the total mass of the monomer (a) and the monomer (b).
The content of 2-methoxyethyl methacrylate in the monomer (b2) (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).

Notable points are as follows.
(1) The content of the monomer (a) is 30 to 50% by mass in the copolymer A and 30 to 40% by mass in the copolymer B, both of which are relatively small amounts.
(2) In the copolymer A, the monomer (b) contains 2-methoxyethyl acrylate, and in the copolymer B, the monomer (b) contains 2-methoxyethyl methacrylate.

  Thus, the present invention uses two types of copolymers having a relatively small proportion of silyl ester monomer units, one of which contains 2-methoxyethyl acrylate units and the other of which contains 2-methoxyethyl methacrylate. It is characterized by including units. And, as will be shown in Examples described later, by having such characteristics, the hydrophilicity of the coating film is improved, the coating film adhesion property to a highly polar surface such as glass is improved, and the wet and dry cycle is performed. It has the technical effect of improving the resistance in the test. This is equivalent to the technical effect that the adhesiveness at the time of overcoating the surface of the old coating film is improved.

  In the requirement (A1), the content of the monomer (a) is, for example, 30, 35, 40, 45, 50 mass% with respect to the total mass of the monomer (a) and the monomer (b). And may be within a range between any two of the numerical values exemplified here.

  In the requirement (A2), the content of 2-methoxyethyl acrylate is, for example, 15, 20, 25, 30 mass% with respect to the total mass of the monomer (a) and the monomer (b). , And may be within a range between any two of the numerical values exemplified here. The monomer (b) of the copolymer A may contain 2-methoxyethyl methacrylate, but the content of the monomer (b) of the copolymer B is the amount of 2-methoxyethyl methacrylate. The content is preferably smaller than the content, and is preferably 1/2 or less of the content of 2-methoxyethyl methacrylate in the monomer (b) of the copolymer B. The monomer (b) of the copolymer A preferably does not contain 2-methoxyethyl methacrylate.

  In the requirement (B1), the content of the monomer (a) is, for example, 30, 35, 40 mass% with respect to the total mass of the monomer (a) and the monomer (b). It may be within a range between any two of the numerical values exemplified in.

  In the requirement (B2), the content of 2-methoxyethyl methacrylate is, for example, 30, 35, 40, 45, 50 mass% with respect to the total mass of the monomer (a) and the monomer (b). And may be within a range between any two of the numerical values exemplified here. The monomer (b) of the copolymer B may contain 2-methoxyethyl acrylate, but the content of the 2-methoxyethyl acrylate of the monomer (b) of the copolymer A is The content is preferably less than the content, and is preferably 1/2 or less of the content of 2-methoxyethyl acrylate in the monomer (b) of the copolymer A. The monomer (b) of the copolymer B preferably does not contain 2-methoxyethyl acrylate.

  In the copolymers A and B, the monomer (b) may contain a silyl ester other than the monomer (a). In that case, the content of the total silyl ester with respect to the total mass of the monomer (a) and the monomer (b) is, for example, 30 to 60 mass%, and specifically, 30, 35, 40, 45, for example. , 50, 55, 60% by mass, and may be in a range between any two of the numerical values exemplified here. The content of the silyl ester other than the monomer (a) is preferably smaller than the content of the monomer (a), and is 1/2 or less of the content of the monomer (a). Is preferable and 1/5 or less is more preferable.

  The content of the copolymer A is preferably 25 to 75 mass% with respect to the total mass of the copolymer A and the copolymer B. In this case, the effect of improving the resistance in the wet and dry cycle test is remarkable. Specifically, the content of the copolymer A is, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mass%, and any one of the numerical values exemplified here 2 It may be in the range between two.

<Synthesis of Copolymers A and B>
The copolymers A and B can be obtained by copolymerizing a mixture of the monomer (a) and the monomer (b). The copolymerization is performed in the presence of a polymerization initiator, for example.

  The weight average molecular weight of the copolymers A and B is preferably 5,000 to 300,000. When the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels off or cracks, and when it exceeds 300,000, the viscosity of the copolymer solution increases and the handling becomes difficult. . This weight average molecular weight is, for example, 5,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000, 300,000, and any two of the numerical values exemplified here are used. It may be in the range between.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2′-azobisisobutyrate. Azo compounds such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, 1,1,3 , 3-tetramethylbutylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used alone or in combination of two or more. As the polymerization initiator, 2,2′-azobisisobutyronitrile and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferable.

  The molecular weight of the triorganosilyl ester-containing copolymer can be adjusted by appropriately setting the amount of the polymerization initiator used.

  Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like. Of these, solution polymerization is particularly preferable in that the copolymer can be synthesized easily and accurately.

  In the polymerization reaction, an organic solvent may be used if necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene, ethylbenzene and toluene. Aliphatic hydrocarbon solvents such as hexane and heptane. Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate. Alcoholic solvents such as isopropyl alcohol and butyl alcohol. Ether-based solvents such as dioxane, diethyl ether, dibutyl ether. Examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, aromatic hydrocarbon solvents are particularly preferable, and xylene is more preferable. These solvents may be used alone or in combination of two or more.

  The reaction temperature in the polymerization reaction may be appropriately set depending on the type of the polymerization initiator and the like, and is usually about 70 to 120 ° C, preferably about 70 to 100 ° C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

1-2. Antifouling agents Examples of antifouling agents include inorganic agents and organic agents.
Examples of the inorganic agent include cuprous oxide, copper thiocyanate (general name: copper rhodanide), and copper powder. Among these, in particular, cuprous oxide and rhodan copper are preferred, and cuprous oxide having a surface treated with glycerin, sucrose, stearic acid, lauric acid, lysine, mineral oil, etc. has a long-term stability during storage. Is more preferable.
Examples of the organic drug include 2-mercaptopyridine-N-oxide copper (generic name: copperpyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate (generic name: zineb). ), 4,5-Dichloro-2-n-octyl-3-isothiazolone (generic name: Sinaine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4-. t-Butylamino-6-cyclopropylamino-s-triazine (generic name: Irgalol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole Generic name: medetomidine), and the like.
These antifouling agents can be used alone or in combination of two or more.

1-3. Other additives Further, the resin for antifouling paint of the present invention may be added with an elution regulator, a plasticizer, a pigment, a dye, a defoaming agent, a dehydrating agent, a thixotropic agent, an organic solvent or the like as necessary to prevent the resin. Examples of dissolution modifiers that can be used as stain paints include rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. , Monocarboxylic acid and salts thereof, or the alicyclic hydrocarbon resin. These can be used alone or in combination of two or more.
Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. Examples of the alicyclic hydrocarbon resin include commercially available products such as Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.).
Examples of the plasticizer include phosphoric acid ester, phthalic acid ester, adipic acid ester, sebacic acid ester, epoxidized soybean oil, alkyl vinyl ether polymer, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, polybutene. , Tris (2-ethylhexyl) trimellitate, silicone oil, liquid paraffin, chlorinated paraffin and the like. These can be used alone or in combination of two or more.
Examples of the dehydrating agent include synthetic zeolite adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, carbodiimidazoles and the like. These can be used alone or in combination of two or more.

2. Method for Producing Antifouling Paint Composition The antifouling paint composition of the present invention uses, for example, a mixed solution containing a copolymer A, a copolymer B, an antifouling agent, and other additives by using a disperser. It can be produced by mixing and dispersing.
The mixed solution is preferably a solution in which various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent.
As the disperser, for example, one that can be used as a fine pulverizer can be preferably used. For example, a commercially available homomixer, sand mill, bead mill and the like can be used. Further, the mixed liquid may be mixed and dispersed by using a container equipped with a stirrer to which glass beads for mixing and dispersing are added.

3. Antifouling Treatment Method, Antifouling Coating Film, and Painted Material The antifouling treatment method of the present invention forms an antifouling coating film on the surface of a film-forming target using the above antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the coating film surface is constantly renewed, so that adhesion of aquatic fouling organisms can be prevented.
Examples of the film forming object include ships (especially ship bottoms), fishing gear, underwater structures and the like.
The thickness of the antifouling coating film may be appropriately set according to the type of the film-forming material, the navigation speed of the ship, the seawater temperature, and the like. For example, when the material to be coated is the bottom of a ship, the thickness of the antifouling coating is usually 50 to 700 μm, preferably 100 to 600 μm.

Hereinafter, the features of the present invention will be further clarified by showing Examples and the like. However, the present invention is not limited to the examples.
In each Production Example, Comparative Production Example, Example and Comparative Example,% means mass%. The viscosity is a measured value at 25 ° C., and is a value obtained by a B-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC. The conditions of GPC are as follows.
Device: Tosoh Corporation HLC-8220GPC
Column: TSKgel Super HZM-M 2 flow rate: 0.35 mL / min
Detector ・ ・ ・ RI
Column temperature bath temperature ・ ・ ・ 40 ℃
Eluent ... THF
The heating residue is a value measured according to JIS K 5601-1-2: 1999 (ISO 3251: 1993) "Paint component test method-heating residue".
The unit of the blending amount of each component in the table is g.

<Production Example 1 (Production of copolymer solution SA-1)>
After charging 400 g of xylene into a 2000 ml flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, the temperature was raised to 83 to 87 ° C. under a nitrogen atmosphere, and 150 g of triisopropylsilyl methacrylate was stirred, 83 g of a mixed solution of 37 g of ethyl acrylate, 238 g of methyl methacrylate, 75 g of 2-methoxyethyl acrylate, and 5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O manufactured by NOF CORPORATION) The solution was added dropwise over 1 hour while maintaining at -87 ° C. After the dropping, 0.5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every hour while maintaining the temperature at 83 to 87 ° C. to complete the polymerization reaction, and then xylene was added. Copolymer solution SA-1 was obtained by adding and dissolving 100 g. The heating residue of the copolymer solution SA-1 was 49.8%, and the weight average molecular weight was 52,000.

<Production Examples 2 to 20, Comparative Production Examples 1 to 4>
Polymerization was carried out in the same manner as in Production Example 1 using the organic solvents, monomers and polymerization initiators shown in Tables 1 to 3 to obtain copolymer solutions SA-2 to SA-10 of copolymer A. Copolymer solutions SB-1 to SB-10 of the polymer B and copolymer solutions T-1 to T-4 of other copolymers were obtained. The heating residue and weight average molecular weight of each of the obtained copolymer solutions were measured.
The results are shown in Tables 1 to 3.

<Production Example 21 (Production of rosin metal salt solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene were placed in the flask, and further 120 g of zinc oxide so that the resin acid in the rosin formed a zinc salt. Was added and refluxed and dehydrated under reduced pressure at 70 to 80 ° C. for 3 hours. Then, it cooled and filtered and the xylene solution of rosin zinc salt (dark brown transparent liquid, solid content 50%) was obtained. The heating residue of the obtained solution was 50.4%.

<Production Example 22 (Production of hydrogenated rosin metal salt solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Hypeal CH2 and 360 g of xylene are placed, and 120 g of zinc oxide is added so that the resin acid in the rosin forms a zinc salt. It was refluxed and dehydrated under reduced pressure at 80 ° C. for 3 hours. Then, it cooled and filtered and the xylene solution of rosin zinc salt (dark brown transparent liquid, solid content 50%) was obtained. The heating residue of the obtained solution was 50.3%.

<Examples 1 to 83, Comparative Examples 1 to 14>
Using the copolymer solutions SA-1 to SA-10, SB-1 to SB-10 and T-1 to T-4, antifouling coating compositions were prepared according to the formulations shown in Tables 4 to 14.

(Coating film wet & dry cycle test)
A glass plate was coated with the antifouling coating composition using a 400 μm applicator to obtain a test plate.
This test plate was subjected to a test in which a 12-hour 40 ° C. fresh water immersion test and a 12-hour air exposure test were repeated for 6 months, and then the physical properties of the test plate were visually evaluated.
Those without peeling were marked with ◯, and those with peeling were marked with x.

  Details of the dissolution modifier, the plasticizer, the antifouling agent, and other additives in Tables 4 to 14 are as follows.

<Elution regulator>
Rosin metal salt solution: the one produced in Production Example 21 is used Hydrogenated rosin metal salt solution: The one produced in Production Example 22 is used Gum rosin solution: 50% solid content of Chinese gum rosin (WW) xylene solution Hydrogenated gum rosin solution : 50% solid content xylene solution of trade name "HYPER CH" (manufactured by Arakawa Chemical Industry Co., Ltd.)

<Plasticizer>
Chlorinated paraffin: trade name "Paraffin chlorinated (Cl: 40%)" (manufactured by Wako Pure Chemical Industries, Ltd.)
E-2000H: Epoxidized soybean oil: Product name "SANSOCIZER E-2000H" (manufactured by Shin Nippon Rika Co., Ltd.)
Tris (2-ethylhexyl) trimellitate: Product name "Tris (2-ethylhexyl) trimellitate" (manufactured by Tokyo Chemical Industry Co., Ltd.)
Hexamol (registered trademark) DINCH (registered trademark): BASF, non-phthalic acid plasticizer

<Antifouling agent>
Cuprous oxide: Product name "NC-301" (manufactured by Nisshin Chemco Ltd.)
Copper pyrithione: Product name "Copper Omagine" (manufactured by Arch Chemical Co., Ltd.)
Zinc pyrithione: Product name "Zinc Omadin" (Arch Chemical Co., Ltd.)
Zineb: Product name "Zineb" (manufactured by SIGMA-ALDRICH)
SeaNine: trade name “Sea Nine 211” 4,5-dichloro-2-n-octyl-3-isothiazolone (solid content 30% xylene solution, manufactured by Rohm and Haas)
medetomidine: trade name "4- (1- (2,3-Dimethylphenyl) ethyl) -1H-imidazole" (manufactured by Wako Pure Chemical Industries, Ltd.)
Econia: trade name "Econea 028" 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

<Other additives>
Talc (Matsumura Sangyo, Crown Talc 3S)
Zinc oxide (Shodo Chemical, 2 types of zinc oxide (trade name))
Bengal (TODA COLOR EP-13D, manufactured by Toda Pigment)
Titanium oxide (Furukawa Kikai Metal, FR-41)
Tetraethoxysilane: Product name "Tetraethyl Orthosilicate" (manufactured by Tokyo Kasei Co., Ltd.)
Aliphatic amide thixotropic agent: trade name "Disparlon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)

<Discussion>
From Tables 4 to 14, the coating film formed using the coating composition of the present invention (Examples 1 to 83) is more glass than the coating film formed using the coating composition of Comparative Examples 1 to 14. The adhesion of the coating film to the surface is improved, and the coating film is not peeled off after the wet and dry cycle test (6 months).

  On the other hand, the coating films formed by using the coating compositions of Comparative Examples 1 to 14 have poor adhesion to the glass surface, and peeling of the coating film occurs after the wet & dry cycle test (after 3 months). There is.

Claims (1)

An antifouling coating composition containing a copolymer A, a copolymer B and an antifouling agent, comprising:
The copolymers A and B are each obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a),
The monomer (a) is represented by the general formula (1),
General formula (1):
(In the formula, R ¹ is hydrogen or a methyl group, R ² , R ³ , and R ⁴ are selected from a branched alkyl group having 3 to 8 carbon atoms and a phenyl group, and may be the same or different.)
The copolymer A satisfies the following requirements (A1) to (A2),
The copolymer B is an antifouling coating composition that satisfies the following requirements (B1) and (B2).
(A1) The content of the monomer (a) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).
(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b). .
(B1) The content of the monomer (a) is 30 to 40 mass% with respect to the total mass of the monomer (a) and the monomer (b).
(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b). .